Terpene resins



Patented Nov. 15, 1949 signor to Hercules Powder Company, Wilmington,Del.,,a, corporation ofDelaware No Drawing. "Application September 4,1945, Serialhlo. 614,432

"11 mains. Xol. 260-824) This invention relates to-new resinouscompositions of matter and to processes for their production. Moreparticularly, it relates, to .res-' ins prepared by the copolymerizationofv a terpene with 1,3-butadiene or a suitable derivative thereof. ITerpenes have been known to polymerize t products which vary in physicalcharacteristics from viscous oils to soft resins at room temperature.specifically, whendipentene or a terpinene, dissolved in ethylenedichloride,.is contacted with catalysts, such as, boron trifluoride,aluminum chloride, etc. for a period'of 27 hours and at a temperature ofC. to 0., a polymer- Y ized product results which is a viscous oil. Whenalpha-pinene, on the other hand,.is contacted with the same catalystunder similar conditions,

except that a reaction period of 40 hours. is employed, a soft resinousproduct results which has a drop melting point between about C. andabout C. Other catalysts and varied-'condi-.

tions for the polymerization may be; employed,

however, it has been found impossible to produce appreciable yields ofresins having drop melting,

points above C.,v and it. is unusual that a resin having this maximummelting point is obtained. This condition is quite-a disadvantage inconnection with the use of these terpene polymers;

in protective coating compositions. The disadvantage rests in the factthat the use of these materials contributes poor drying, properties ,to.

the coating compositions. While the .use of these polymers assubstitutes for ester'gum givesimproved resistance to discolorationunderiultra violetlight and improved gasproofness, etc. to

protective coating compositions, thedrying properties of the coatingcompositions are so inferior that they constitute 52. serious impediment.to

their commercial acceptability.-

Furthermore, the alkali resistance of protective coatings containingterpene polymers has been ,-found to be inferior to that of ,ester gumcontaining protective coatings...

water resistance to the resulting coatings than does ester gum, thewater resistance of protec- And. although. the use of these newmaterials.contribute better-x tive coatings containing these polymers isinferior to that of coatings containing, for example, rosin-modifiedmaleate resins, rosin-modified glyptal rosins, and urea formaldehyderesins.

Generally, when a terpene or a mixture of terpenes is subjected toconditions which are con- J ducive to polymerization, the polymersformed are of very low order or degree. Actually, the polymers formedare usually the dimer, the tri- 2 mer, and the tetramer along with smallamounts of higher polymers. The dimer willusually be found topredominate over the otherpolymers formed. The significant fact isthatthe. average,

degree or order of polymerization will be rather low. For example, theaverage degreev of polymerization as determined on a weight basis may;vary between 2.0 and about 4.0., These values,- it will be understoodare based on polymerizates.

which have been treated to remove substantially all of the unpolymerizedconstituents. In other words, the polymerizates will consist substantiallyentirely of the dimer, trimer, etc. of the constituent orconstituents being polymerized with;

substantially none of themonomer being present..

It is an object of this invention to provide new resinous. products.which possess generally higher viscosities or melting points, as thecase may be, 1

than the polymers of terpenes or terpene mixtures of the prior art. Itis a further particular object of the invention to provide new resinousproducts which are solid at room temperature.

It is a further object to provide terpene-com taining resinous polymers,which are characterized by their having a relatively high degree ofpolymerization when compared with the terpene-;

containing polymers of the prior art.

A further object of the invention is to provide resinous products whichare characterized by their possessinggood water and alkali resistance.Also, it is an object, to prepare resinous products which whenincorporated into protective coatings will yield protective films havinggood water and alkali resistance.

An additional object is products whichwhen incorporated into protectivecoatings will yield protective films having good drying characteristics.It is particularly desired to exceed the characteristics of protectivecoatings containing the terpene polymers of the prior art. H

Other objects will appear hereinafter. In accordance with thisinvention, it has been found that variousterpenes ormixtures thereof maybe copolymerized with various compounds having the following generalformula: 8

wherein R1 is hydrogen, halogen or an alkyl radial of not more than 2carbon atoms; R2 is hydrogen, halogen, phenyl or an alkyl radical of notmore than '7 carbon atoms; R3 is hydrogen, halogen or an alkyl radicalof not more than 7 carbon Ito provide resinous v 3 atoms; where R4 ishydrogen or an alkyl radical of not more than 2 carbon atoms. Thepolymerization reaction will be carried out in the presence of asuitable catalyst and under suitable operating conditions to yieldresinous materials which have many distinguishing characteristics overthe resinous polymers of terpenes or mixtures thereof.- Thesenew-copolymersare unusual in that they possess generally higherviscosities In place of pure terpenes or their synthetic mixtures, it ispossible to employ naturally-occurring terpene mixtures. Thus, forexample, it is possible to employ either wood or gum turpentine. Woodturpentine consists primarily of alpha-pinene, whereas gum turpentine,depending uponits; source, will..-contain varying proportions ofalpha-andtbeta pinenep Botli: wood and gum turpentine make excellent rawmaterials to or melting po as e ase may be, than thee-lei employ inaccordance with the invention. Other resinous polymers produced by thepolymerization of terpenes or terpene mixtures.

Thus, it is'pos sible in accordance with thisinventionitotprcpare.products which are viscous liquids-or-solids-which'=.

fractions containing crude mixtures of various terp'enes and obtained asa result of the recovery ofuol'eoresin'ous'imaterial from pine wood maybe employed; Onesuclr. commercially available terhave melting points asdetermined by the drop" m pene containing mixture is known as Solvenol.

method of from about C. up to about-160 (1.,

preferably, between about C. and about;ll C. The average degree ofpolymerization of these new copolymers will be found to besubstantially" higher than that of products resulting when terpenes orterpene mixtures are l-polymerizedsunder asuitable de'rivativethereon;Thus, for example;

there-may be employed ..1;3-butadiene; alk-yl sub:- stituted 1;3butadienes,isuch as, (2-methylf- 1,3 buta'diene) (2,3'-dimethyl I1;3-butadiene) (2- ethyl -1,3-butadiene) (2.,3'diethyl 1,3-'butadi'n'e);(2 m'ethyl --:3-ethyl 1,3-butadienei,

(2'-propyl 1,3-b'utadiene).; (2,3dipropyl 1,3- butadiene) (2 methyl"'-3'-propyl -1;3 -:butadiene) (Z ethyI' B -propyI 1,3-butadien'e)(2i-heptyl- 1,3-butadiene), etc.; butadienes, such-as; (2'-'chloro1,'3'-'"butadiene), (2 bromo 1,'3 butadien-e) (Zeiodo- 1,3-butabrorno---1';3-butadiene); (2,3-diiod'oz 1,--3'-'-buta- (1,2,3-trichl0ro1,3E-b'utadiene'), etcr; substituted lfi-butadienes,- such as, 2 phenyl-1,3? butadine etcx; alk yl and halogen substituted 1;3 butadie'nes,-such as; (2 chloros -3-methyl" in' the copolymerization'with a desiredte'rpene;

terpene 'hydroca'rbonshavingthe empirical for mul'a cioHis,or'a-'mixture-th'ereof, may be copolymerized with 1,3-butadiene or a'suitable derivative thereof as-hereinbefore described to produce newresinous products in accordancewith penes, such as, dipentene,alpha-terpinene, betaterpinene, gamma-terpinene, terpinolene,sylvestrene, alpha-phellandrene, beta-phellandrene,

the: carenes; alpha-pinene,-=.. betapinene,

gammaefenchene etcc,

2Q erization of alphaand/or beta-pinene.

39 {from alphaandibeta-pinene.

halogen substituted 1,3'-'- This particular mixture contains themonocyclic terpenehydrocarbons, terpinene, terpinolene, and

dipentene. Other terpene mixtures which may beemployed are thoseobtained in the heat isom- When, forztexample;:,alpha+.pinene is heatedat elevated temperature it1uis ;possible to obtain products containingas: much as- 40%. allo-ocimene along? with substantial 'f amounts ofalpha+pinene,' di

25.1 pentene and other complex terpene :product's; Suitable pyrolysis ofbeta-pinene yields myrcene.

togetherfwithzvarious :monocyclic terpenes. Still further, it ispossible .toemploy terpene. mixtures obtained' in the synthesis ofethersandcalcohols Anyj of these byproduct 5 mixtures: containingsubstantial quantitiesgieven'; though: they may not rconsist renti'rely,ofitterpenes,maysbez-suitablycemployed 'asythe' terspeneraw-materialsiof the present invention.

35:, In accordancenwith the 'present invention ,a

mixturezof aliterpene and butadieneor a'substitutiomproductthereof-izdesirablyrin .thepresence oftan inert solventpis. contacted:with apolymer izationforxcondensationtcatalyst'at a temperature 411;which.promotes .'thexopolymerization' ofithe' condine) (2-cliloro'3-b'romo-1 1,3--butadieue) phenyl stituentsjoraperiod suflicientlmlong.to securea substantial yieldi-of copolymerizedaproduct. De-

sirablm'the' reactionrmixture :will be vigorously.

agitatedzthroughout the'speriodu of contact of the 2 5;; reactantszwithihe catalyst;

L B -Hutadiene); 1 metl'iyl 2"-chloro 1 ,3-b'uta' dine), (2 bromo'-3-'methyl"-- 1,3- butadiene), (2-iodo 3-methyl 1;3=butadiene-)(ZL-Tchloro Thefipolymerization catalystszwhich willbeemployediinaccordance withtthis invention comprise."

thee metal .iha-lidess, of? the -:welleknown Friedelcraftsx type,such::as,-3 boron trifluoride'z and. its highly unsaturated 'comp'ounds;such" as, (3,4---5o;molecular complexesxwith:ethers-and acids, ti--di'chloro 1,2 j ifi hexatetraenel', (l 'c hloro 1,2, 3 f5-hexatetraene)and! 1'E4-di'chloro '-*2 ,3;5 -hexa- A tiiene) may be employed? Ifdesired, a mixture-=- of-"severalofthe abovecompounds may be em---ployed instead of a single one of said compounds tanium rchloride;ferric chloride, and'the chalides of metals awhosehydfoxidesi'areramphoteric, as aluminum: chloride; stannicxcliloride',zinc Chloe rider-etc; V

It will b'e realized that ihesopcrable ranges for V theacatalyst'itoJreactant iratiosyireaction:ttemperae actiorrztak'es; places. preciselyascertained.

beyond: which .L-it iwouldc not i be economically: de-

sirable "to -operates. Hnce','..g'enerally, iniaccord-wanceawitirthetinventiorrz the :catalyst to'reac'ta'nt I ratim-mam'vary;betwenxaboutrODOl and about. the invention: Thus, for example,=-I mayen1-plcy-' 65.; 1.0::- The *Operablestemnerature: may; vary: fromacyclic terpen'es; such as, myrcen'e;'--ocimene; all'o-f ocimene,cryptota-enene; -etc:;" monocycl-ic t er-*- about"- 60- C.:to2:about-+-200 0.; and-the opera.

ble';reactioniperiodwwill i-varyzfrom about 1 to about1400rhourssHowever; .it .=is preferred .zwhenv a 1metalrhali'de:ofr rthe--Eriedel.- Crafts type :is -:em-

ployedy tousearcatalystto reactant ratio between about0:02:andabout:0:25, area'ction temperature between-'about20".-:-C'.f:and about-F809 C., and

a reaction period between: about: 2" hours 1 and about 24 hours.

s. In: accordance l-with -:thiscinventiommtheemetal.,

halide catalyst is employed'ineonjunction with' a halogenated inertsolvent for the reactants. "It. has been found that when a' metal halidecatalyst of the Friedel-Crafts type is employed for the granules. Forexample, ethyl alcohol or acetone may be so employed with many of thecopolymers prepared in accordance with this invention.

The color of the final products may be im-' with an organic liquid whichis miscible with the inert solvent employed in the reaction but in whichthe copolymer is insoluble. After vigorous agitation, the copolymer isprecipitated from the copolymerization. m conjunction with an inert 5proved by utilizing terpenes which have been' halogenated solvent,.employing a catalyst to redistilled from caustic. Also, the use of aninert actant ratio, a temperature and a reaction period atmosphere suchas CO2, N2, etc. during the rewithin the-broad operable ranges disclosedhereaction period leads to the production of pale inabove, generallysolid polymers'will result. colored products.- Further refinement ofthe. The ratio of terpene to butadiene or substituproducts may beaccomplished by treatment with tion product thereof may vary widelydepending adsorbents such as silica gel, fullers earth, upon theparticular compounds under considerabauxite, activated carbon, activatedmagnesium tion. Generally, however, it is preferred to emand aluminumsilicates, etc. This treatment reploy the terpene in an amount betweenabout moves traces of combined catalysts and further 5% and about 95% ofthe total weight of the 5 bleaches the products. It may be appliedeither a reactants, .with the butadiene or substitution 1 A before orafter removal of the solvent. Other product being employed in acorresponding refining agents which may be employed include amountofbetween about 95% and about 5% selective solvents, such as, furfural,furfuryl ofjthetotal weight of the reactants. It has been alcohol,phenol, etc. If desired, the copolymer found that as the proportion ofbutadiene or resins obtained in accordance with the processessubstitution product thereof is increased, the redescribed herein may besubjected to vacuum sulting copolymers tend to have higher meltingdistillation to remove volatile copolymers, leaving points and also showa decreasing solubility in copolymer residues having higher meltingpoints dryingand semidrying oils. Generally, it may than the initialcopolymerization product. be said that where the ratio of terpene tobuta- 5 There follow several specific examples which diene orsubstitution product thereof is 2.5 or illustrate particular embodimentsof the pringreater, copolymers result which are soluble in ciples ofthis invention which, however, are in no drying and semidrying oils. wayto be construed as being limiting. All parts .The solvents which may beemployed in conand percentages in this specification and claims junctionwith the metal halide catalystst of the are by weight unless otherwiseindicated. Friedel-Crafts type in accordance with his inventiongenerally comprise any inert saturated P 1 t V halogenated hydrocarbonsuch as methyl chlo- In these examples which follow the procedure ride,methyIenechIOride, chloroform, carbon, was to dissolve dipen e e a d"crude butadiene tetrachloride, ethyl chloride, ethylene dichloride, inethylene de. he crude butadiene em-'- trichloroethylene,tetrachloroethane, and pentaployed Was a mixture containing 50%butadiene chloroethane. The most preferred solvents .for, and,50 butane.In the table which follows, the this reaction are ethyl chloride andethylene difigures" for b-utadiene represe the q y o ch1oride v v V gpure butadiene employed. Anhydrous aluminum' Following the reactiqnperiod,- employingthe 40 chloride was then added 120.1116 5011111011With 0001- conditions as hereinabove described, the reacm a d agitationover a period of 20 minutes while' tionjmixture is suitably treated torecover the the temperature was held at -18 to 10 C. copolymerizationproduct as determined by the. The reaction mixture was then agitatedat'0.,C. particular.- procedure employed in accomplishing for 2 hours;After diluting the reaction mixture the reaction. Thus, the catalyst maybe removed w t 1.7 ti es its Weight of ethyl alcohol the by washing thereaction mixture with water or precipitate was separated, washed withethyl alan aqueous alkali or an aqueous inorganic acid. cohol,redissolved in benzene, and the solution The aqueous'acid wash oftenfacilitates the washed with aqueous 6% HCl. The solution was removal ofmetal halide catalysts from. the ,rethen washed with water to remove theHCl and action mixture since it greatly assists in decomthe solventremoved by vacuo distillation. Furposing complexes which the catalysthas formed ther reaction conditions, yields, and characteriswithunsaturated centers of the materials with tics of the product aredescribed in the following which it has come in contact. Following thetabulation:

' Aluminum Ethylener Color Dro Example %2; gzfig Olggge, Digiggtrsrde;Egg Temperature g g' (81:25:51 hgeg ig 200 62 f 15 4 r x 200 I 31 15 4%3 J? 811:: thi 200 15 15 400 2 -18to 62 WW 70 0.

alkali or acid wash, it is desirable to wash with Examples 4 t 7 waterto remove all traces of alkali or acid. The solvent and any unreactedconstituents are re- 65) In these examples h paflflcular terpene d,moved, desirably by means of vacuo distillation the h 3' w (lsoprene) Wi using if necessary a final bath temperature f. solved in ethylenedichloride. The particular isoabout 170 to 220" 0. An alternative methodfor en m y w an impure materiaiconsiste; recovery of the copolymer afterthe catalyst has of 99% l p e and 10% n T0 been removed is to dilute thereaction mixture resulting 50111151011 0f the terpene d Op 'e e inethylene dichloride was added the aluminum chloride polymerizationcatalyst in the form of a 3.5% solution af aluminum chloride in ethylenedichloride over a period of0.5' to 2.0 hours, with solution, often inthe form of 1 a powder or 7 agitation and cooling, maintaining thetemperagases-cs:

ture below"25"l.C.. iThei reactionzmixtur'e wasithen'ai'lowedi'to:staii-dfforia'periodvotlabout '28rhours at ridemasiused'asthe'solventlin placeof:the ethyl" ene dichloride. The reaction wascarried-out and. the; product isolated as described-inthat: example. Theresidue'rconsisted of 100parts ot'arlight colored solid resin havinga.melting pointtof.-175= C.

" Example '1 2 Eighty-five parts of alpha-pinene were dissolvedin==600': parts of :ethylene-i chloride.

Exam e To: no. arts rene Chloride, 1 Temperature Color Melting m 1 partsparts 2 hours parts Point i .alpha pinene-filll .9 335 28 Dito25 17Brown. 60

"Example 8' maintaining the temperature-'at-IO" to-- 15 "C.,

."Fifty parts of. allo-ocimene (99%. pure) -an'd20." partsof 2-'ch1or01,3-butadiene weredissolvd inl250parts of ethylchloride. Five. partsotanhydrousialuminumchloride were added with agi tation andlcooling at-60'C. to 30 C..over a period of- :75 hour. Agitation was continued at--60 C. to -40 C. for 2 hours. The reaction mixturewas then added slowlyto 700 parts of ethyl alcohol with vigorous agitation. A precipitateformed which was .separated, thoroughly.

washed with ethyl alcohol and dried. The result ing copolymer resin wasobtained in the amount of 62..parts, having a drop meltingpoint of 110 Gand having acolor of 3 Amber. onthe Lovibond color scale.

Example!) Fifty parts of beta-pinene (99% pure) and 20 parts'of 2-chloro1,3-butadiene were dissolved in 250 parts of ethyl chloride- Five. partsofv gaseous boron trifluoride were introduced with agitation and coolingat -60 C. to 30 C. over a period of 0.75 hour. Agitation was continuedat -60 C. to 40 C. for 2 hours. The reaction mixture was slowly added to700 parts of ethyl alcohol with vigorous agitation. A precipitate formedwhich was thoroughly washed with ethyl alcohol anddried. The resultingcopolymer resin was obtained in the amount of 65 parts, having a dropmelting point of 100 C. to 120 C., and having-a color of 5 on theLovibond color scale.

. Example-1 0 Eighty-five parts of dipentene were dissolved in 600 partsof ethylene-dichloride contained in a flaskequipped with a stirringdevice, thermometer and-drying tube. Fifteen parts of pure-1,3-buta--diene were then added, the temperature of the mass being maintained atto C. At the sametemperature and during about minutes 5 parts ofanhydrous aluminum chloride'were added. The reaction mixture wasagitated and held at a temperature of -10 to --15 C. for 5 hours afterwhich it'was hydrolyzed by adding parts of water, 800. parts of benzenebeing added to facilitate the washing of the product. The benzenesolution was washed with 15% aqueous hydrochloric acid and then withwater 4 times at -to 60 'C. to remove the hydrochloric acid. The solventand any unreacted material were removed by distillation in vacuo. Theresidue consiste'dof 1'00 parts of a light-colore'd'solid' resin havingaflmelting point 0f-142 'C.

. Example 11 Example. 10 wasrrepeated' except that ethyl; chlotionmixture was thenwashed with aqueous-15% hydrochloricacid and then 5times-with water-sat 50 to60 C. Thesolvent and any unreacted ma-. terialwas removed by'distillationin vacuo. The residue consisted of parts 1.of a 'palecolored solid resin having a melting point of 57 C.-

"Example 13 Eighty-fiveparts of 95 dipentene was 'dissolved-in 600'parts of chloroform. :Fi'fteerr parts of 98 1,3-butadiene were added:atta -tempera-- tureof --10 to --15C. At the-sametemperature 5 parts ofanhydrous aluminum chloride-were thenadded in'sma'll portions. Afterthe'addition of the catalyst the reaction mixture was agitated at 10" to'15'C. for 5 hours. The: catalyst was hydrolyzed by adding 25 parts ofwater and then -washing thereaction mixture with 15% aqueoushydrochloric acid and therritimes: with waterat50to 60 C. Thesolvent-and unreacted' material were removed bydistillation 'in vacuo-Theresidueconsistedof 51' parts ofa' light-coloredviscous resinous Imaterial which was soluble in benzene; gasoline and other butpractically insoluble in'alcohol and methyl-acetate.

The "resinous copolymers prepared iniaccord ance l with this inventionare characterized by their having heavier viscosities or highermeltingpoints, as the case-may be, than the polymers- .prepared. from variousterpens or terpene mixturesof the prior art. By employing the properconditions, copolymers :can be :prepared which range in melting pointfrom room temperature up to about C. These solid resins have an.extended. scope of utility over the terpene polymjers which aregenerally found to be viscous oils and semisolids at room terperature.

will be 2.5. ,HIt willbe understood; that wherever in this specificationreference is made to the melting point ofa resinous material, a,:melting point as determined. by the Hercules ;drop method is em t Thisapplication-is acontinuation-in-partof my application for United StatesLetters Patent formula "andseniewhatj flexible, and they adhere well tovarious surfaces, such as, woodygl'ass, paper, or

metal. Hence, the resins are very useful in the form o f--their-clearsolutions in the lacquer,

varnish and'adhesive field's. They may also be used the 'formulation ofpigmented coating compositions, such as, paints and pigmentedlac- 'quersfor wood, metal, paper, etc. 'Unpigmented solutions or emulsions of the'copolymer resins are suitable for impregnating or coating paper,

textiles, fibers, wood, etc. tocontribute strength, toughness,flexibility, etc. thereto.

-The solubility characteristics of these new resins are such that'theymay be dissolved in common solvents, such as, gasoline, benzene,toluene, xylene, chlorinated aliphatic and aromatic .11 hydrocarbons,terpe'nes, hydrogenated naphthalene,'etc. vents,-such as, ethyl alcohol,acetone, dioxane, etc.

They are only slightly soluble in sol- ..It willbe understood thatwherever in this specification thedegree. of polymerization is referredto,. there is contemplated the average number on a weight basis ofpolymerizable units Thus,

polymerization, whereas the remainder or 50% of the total polymerizablematerial is converted to. units. .each of which contains three of the.polymerizable units existing prior to polymerization, then the averagedegree of polymerization Serial; No.. 398,108, filed June 14, 1941, 'nowabandoned. H I

What I claim and desire to protect by Letters Patent is:

' 1. The process'which comprises copolymerizing a mixture of a cyclicterpene in an amount within the range of about and about 95% i v tsolution in an inert halogenated hydrocarbon ,containing not more thantwo carbon atoms and of said mixture, and in, complementary amount, anunsaturated compound having the general wherein R1 is a member of thegroup consisting of hydrogen, halogen and alkyl radicals having not morethan two carbon atoms; R2 is a member of the group consisting ofhydrogen, halogen, phenyl, and alkyl radicals having not more than sevencarbon atoms; R3 is a member of the group consisting of hydrogen,halogen, an dalkyl radicals having not more than seven carbon atoms; andR4 is a member of the group consisting of hydrogen and alkyl radicalshaving not more than two carbon atoms, in the presence of a metal halideFriedel-Crafts catalyst for a reaction period of about 1 hour to about400 hours and at a temperature between about -60 C. and about +80 0.,said process being carried out in solution in an inert halogenatedhydrocarbon containing not more than two carbon atoms and I five halogenatoms as a solvent for said mixture. 2. The process which comprisescopolymerizing a mixture of a monocyclic terpene in an amount within thermg'ear about 5% and'about 95% formula of said mixture and, incomplementary amount, an unsaturated compound having the general Raneoam RrRg consisting of hydrogen, halogen, and alkyl radicalshaving-notmore than seven carbon atoms; and R4 is a member of the group consistingof hydrogen and alkyl radicals having not more than two carbon atoms, inthe presence of a metal halide Friedel-Crafts catalystfor areacunsaturated compound having 'mula tion period. of about 1 hour toabout 400' hours and at a temperature between about 60 C. and about +80C., said process being carried out in solution in an inert halogenatedhydrocarbon containing not more than two carbon atoms and =fivehalogenatoms as a solvent for saidmixture.

3.. The process which comprises copolymerizing a. mixture of a bicyclicterpene in an amount within the range of about 5% and about 95%. f saidmixture and, in complementary amount, an

the generalforwherein R1 is a member of the groupconsi'sti'ng x ofhydrogen, halogen and alkyl radicals havin not more than two carbonatoms; R2 is a member of the group consisting of hydrogen, halogen,

phenyl, and alkyl radicals having not more than seven carbon atoms; R3is a member offthe group consisting of hydrogen, halogen, and alkyl,radicals having not more than seven carbon atoms and R4 is a member ofthe group consistling ofhydrogen and alkyl radicals having not more thantwo carbon atoms, in the presence of a metal halide Friedel-Craftscatalyst for a reaction period of about 1 hour to about 400 hours and ata temperaturebetween about C'. and

about +80 C., said process being carried out in 4 five halogen atoms asa solvent for said mixture.

4. The process which comprises copolymerizing a mixture of dipenten inan amount within the range of about 5% and about 95% of said mixtureand, in complementary amount, an unsaturated compound having the generalformula than two carbon atoms, in the presence of a metal halideFriedel-Crafts catalyst for a reaction period of. about 1 hour toabout400 hours and at a temperature between about -60C. and about C.,said process being carried out in solu- 1 1 than aninert= tchlorinated.-:-hydrocarbon--:constaining not moretthanztwo carbon atoms :and five'.:'chlorine1at0ms;-asra solvent for said'mixtu-re.

5. The process which comprises copolymeriz-ing a mixture of a pinene inanamount within the 1 range of about and about 95% of said mixture and,in complementary' amount, an unsaturated rcompound. having the generalformula rwhereinRrgis 2a: memberzofi the igroupsconsisting :of:hydrogen,v halogenrand alkyhradica-ls having mot more: than twocarbonatoms 3R2. is a-member -Of'ZithB cxgroup :consisting of hydrogen,halogen, 'phenyl', and alkyl r radicals having notamoreithan Rseven'carbon atoms; -;R3. is a memberofithegroup -:consisting' of hydrogen,-halogen,..and \alkylriradi- -cals having not more than. .seven carbon.atoms; and Rl is a member of .the'group consistlngxof"-hydrogenandialkyl radicals having not more than two carbon atomsiinthepresence of a metal -halide FriedeFCrafts catalyst 11 for :-.a.c'r-eaction period-of about" lhourto about "4001 hours .and at a 1temperature between about 60 C. and -about-i 80" C., =said process beingcarried out in *Solution in an .inert'ehlorinated 'hydrocarbon-'-containing not more than-' -two carbon atoms -and 1 five chlorineatoms :as. =a=sol-vent for said -mixture. 6. The=processa whichcomprises: copolymerizing a mixture of dipentene in an amount within-therange of about;fx%..landraboute95% of said mixture and, in complementaryamount, 1,3-butadiene, in the presence of .a metal halide Friedel-Crafts catalyst for a reaction period of-about" 1 "'hour to i about-'400*hours and "at a temperature between" about 60 C. and about l 80'0., '-"said "process being-carriedout in solut-ion in an inert"chlorinated hydrocarbon containing "not -more :than two-carbon atomsand five chlorine'atoms *asa solvent'forsaidmixture; I

7."The process-Whichmompriseseopolymefizing a mixture" of dipentenein-an' amount =Within*-t=he range of"*about-'-5% and" about !5%:of-saIdmix- "ture-andrin"complementary-amount, isoprene in the .;presence 0: :a-'metal*ha-lid'e Friedel Craf-ts catalyst. for a. reaction period of*about 1 hour :to about 400 hours-and-at -a: temperature between t.ure"am l,;;1n 1 complementary .eamount, 1,3:buta- -diene,'i in. .thepresence: of ametaL- hazlide-FriedelmCrafts catalystzfor a:reaction;periorl;:ofeabout; 1 ;hour.;to:about400 hoursandcatzawtemperaturebe--;tween-::.-about +6020...:and.:.-about +8O 1C --sald5;:191i0085sizb8i11g carried; outzinvsolution;ina'an. ert achlorinated,.:hydrocarbon 1 containing xnot nmcre .zthan tworca-rbon 1-:atoms-andfive-;.ch1orine::atoms 47351 .185 solventgromsaidrmixture.

9. The process whiclrcomprisesxopolymerizinQ nazinixtnre of;dipenteneinz an amount-within? the ;:range :ofsabout- 5.%:. and :;aboutofxsaldsmix- -5turez-and, 11in. rcomplementary amount, 11335131128.-idiene,:-in1the :presemee ofzaz metal:11alide- Friedel Grafts; catalyst:for :a; IEB-CfiOIIiPEIi-Qd iofrabouti2 -:hours torabont 24qhours andtatatemperaturezbertween ;.about -'.i20 .C. and about .-|-:80 20.;ssaid'irpnocess;;beingr;carrie'd outrin:"solution.- inaethylene-:dichloride;asset-solvent forzsaid mixture.

:10. .2The..:proc.ess:;which:comprises cop'olymeriz- 'ing: armixturec of.1 dipentenelinnan' zamountzw ithin." therrangecofvabout 5%:andab0utta95:%.:ot:said rxmixture'san'd, 'incomplementaryzamount;:isoprene, in the: presence: :of 1a: metal'shalid'eFriedelt-traits catalyst ion-a reaction periodrofaabout Zl'l'hQHIZSLtO"about :24 --hours andvxat a itemperaturelvbetween :about 420 C." andabout 4 380 C.;-said:proeess besing carriedoutin solutioniain ethyleneadichloride as a solvent 'fOI- SEI'id mixture.

i 11'. The process yvhiclrvcomprises:copolymerizing axmixture .1 ofaipha=pinene in -anamount with-in the -range of about 5% and about"= 95of said mixture and, in complementary amount, I-,-3-buta'diene,- in thepresenceof armetal halide 1i Frie'd'eI Crafts cataylst' for a reactionperio'dof about 2lhours -to about 24' hour-s and at a. tem- --perature'=between' about --20 C.=andabout -F'80 0., said process being carriedout in solution dn ethylene dichloride as a sclvent for said mixture.

mm) Lsnummnmsenae.

'KREFERENGESLGITED V The following references-are -of. .recordgm 'theffile .of this patent:

i STA'IES PATENTS Number Name 7 .I, Date 2 ,092,295 "Van" Peski"Sep.t.f17,.1937 2,119,976 Wilson June'"7,"1938 2,384.400 RummelsburgSept. 4, 19-15

